JPWO2017155106A1 - Fluororesin composition, molding material and molded article - Google Patents

Abstract

Provided is a fluororesin composition which is excellent in flexibility and oil resistance, hardly discolored by heat, and excellent in moldability.
A fluororesin composition comprising a melt-kneaded product comprising a fluorine-containing elastomer having a storage shear modulus G ′ of 100 or more and a melt-moldable fluororesin having a melting point of 150 ° C. or more, wherein the fluorine-containing elastomer comprises the fluorine It is dispersed in the resin, the content of the fluorine-containing elastomer with respect to the total of the fluorine-containing elastomer and the fluorine resin is 10 to 65% by mass, the total amount of the fluorine-containing elastomer and the fluorine resin, The fluororesin composition, wherein the storage elastic modulus E ′ of the fluororesin composition is 250 kPa or less at a temperature of 90% by mass or more with respect to the fluororesin composition and at a temperature 25 ° C. higher than the melting point of the fluororesin.

Description

  The present invention relates to a fluororesin composition, a molding material, and a molded body.

Fluorine-containing elastomers such as tetrafluoroethylene / propylene copolymer (hereinafter also referred to as “TFE / P copolymer”) have heat resistance, oil resistance, chemical resistance, electrical insulation, flexibility, etc. As an elastomer material having excellent characteristics and capable of radiation crosslinking, it is used for hoses, tubes, gaskets, packings, diaphragms, films or sheets, wire covering materials, and the like.
Further, in order to supplement the characteristics of the fluorine-containing elastomer, blending of the fluorine-containing elastomer and a fluorine resin such as an ethylene / tetrafluoroethylene copolymer (hereinafter also referred to as “E / TFE copolymer”) may be performed. Has been done.

For example, in Patent Document 1, a TFE / P copolymer and an E / TFE copolymer are blended to improve mechanical properties such as tensile strength and tear strength, and properties such as toughness. In Patent Document 1, in addition to the TFE / P copolymer and the E / TFE copolymer, an ethylene-acrylic acid ester copolymer or an ethylene-vinyl acetate copolymer is used in addition to the TFE / P copolymer and the E / TFE copolymer. A large amount of polymer is blended.
Moreover, in patent document 2, in order to improve the cut-through property of TFE / P copolymer (characteristic that it is difficult to soften at high temperature), together with TFE / P copolymer and calcium carbonate, E / TFE copolymer and Is blended.
Also in Patent Document 3, a TFE / P copolymer and an E / TFE copolymer are blended for improving the cut-through property. And in patent document 3, since there is too much E / TFE copolymer blended with the TFE / P copolymer, flexibility and elongation decrease, so the blending amount of the E / TFE copolymer with respect to the whole blend polymer is It is 40 mass% or less.

JP-A-5-78539 Japanese Patent Laid-Open No. 10-334738 JP 2010-186585 A

For example, a material used for a harness in an automobile engine room is required to have excellent flexibility in order to ensure the wiring freedom of the harness. However, as pointed out in Patent Document 3, in order to suppress flexibility and decrease in elongation and ensure flexibility, the ratio of the E / TFE copolymer blended with the TFE / P copolymer is lowered. There was a need to do. However, if the ratio of the content of the fluororesin to the fluoroelastomer is lowered, the oil resistance to lubricating oil such as automatic transmission oil may not be sufficient.
In addition, when a fluorine-containing elastomer and a fluororesin are blended, thermal discoloration may occur under heating. In this case, the degree of freedom with respect to the colorability of the molded product is narrowed. Further, when the moldability is not sufficient, there may be a defect due to molding failure such as a weld line in the molded body.

This invention is made | formed in view of the said situation, Comprising: It becomes a molded object which is excellent in a softness | flexibility and oil resistance, and is hard to be discolored thermally, and it aims at providing the fluororesin composition excellent in moldability. .
Moreover, this invention makes it a subject to provide the molding material and molded object using the said fluororesin composition.

The present invention has the following configuration.
[1] A fluororesin composition comprising a melt-kneaded product containing a fluorine-containing elastomer having a storage shear modulus G ′ of 100 or more and a melt-moldable fluororesin having a melting point of 150 ° C. or more,
The fluorine-containing elastomer is dispersed in the fluororesin,
The content of the fluorine-containing elastomer with respect to the total of the fluorine-containing elastomer and the fluorine resin is 10 to 65% by mass,
The total amount of the fluoroelastomer and the fluororesin is 90% by mass or more based on the fluororesin composition,
A fluororesin composition having a storage elastic modulus E ′ of 250 kPa or less at a temperature 25 ° C. higher than the melting point of the fluororesin.
[2] The fluororesin composition is a fluororesin composition comprising a melt-kneaded product containing an ethylene copolymer derived from an ethylene copolymer having an epoxy group, the fluoroelastomer, and the fluororesin, The fluororesin composition according to [1], wherein the content of the ethylene copolymer is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the fluorine-containing elastomer and the fluororesin.
[3] The fluororesin composition according to [1] or [2], wherein the fluorine-containing elastomer is a copolymer having units based on tetrafluoroethylene and units based on propylene.
[4] The fluororesin composition according to any one of [1] to [3], wherein the fluorine-containing elastomer forms a sea-island structure or a co-continuous structure and is dispersed in the fluororesin.
[5] The fluororesin is a polymer having a unit based on tetrafluoroethylene, a polymer having a unit based on vinylidene fluoride, or a polymer having a unit based on chlorotrifluoroethylene. ] The fluorine resin composition in any one of.
[6] The fluororesin composition according to [5], wherein the fluororesin is a copolymer having units based on ethylene and units based on tetrafluoroethylene.
[7] The fluororesin composition according to any one of [1] to [6], wherein the fluororesin has a melting point of 150 to 300 ° C.

[8] A raw material containing a fluorine-containing elastomer having a storage shear modulus G ′ of 100 or more, a melt-moldable fluororesin having a melting point of 150 ° C. or more, and an ethylene copolymer having an epoxy group is melt-kneaded and cooled. A method for producing a fluororesin composition,
In the raw material before melt kneading, the content of the fluorine-containing elastomer with respect to the total of the fluorine-containing elastomer and the fluorine resin is 10 to 65% by mass, and the total amount of the fluorine-containing elastomer and the fluorine resin is, It is 90 mass% or more with respect to the said fluororesin composition, and the content of the ethylene copolymer which has the said epoxy group is 0-10 mass with respect to a total of 100 mass parts of the said fluorine-containing elastomer and the said fluororesin. Department,
After the melt kneading, the fluorine-containing elastomer is dispersed in the fluororesin, and the storage elastic modulus E ′ of the obtained fluororesin composition at a temperature 25 ° C. higher than the melting point of the fluororesin is 250 kPa. The manufacturing method of the fluororesin composition characterized by the following.
[9] The method for producing a fluororesin composition according to [8], wherein the fluorine-containing elastomer is dispersed in the fluororesin so as to form a sea-island structure or a co-continuous structure.
[10] A molding material comprising the fluororesin composition according to any one of [1] to [7].
[11] A molded product obtained by melt molding the molding material of [10].
[12] A molded body composed of a film, sheet, hose or tube having a single layer or a multilayer structure, and at least one of the layers in the molded body is a layer formed by melt molding of the molding material of [10]. , Molded body.
[13] A covered electric wire having a conductive wire and a covering material, wherein the covering material is a covering material formed by melt molding of the molding material of [10].

The fluororesin composition of the present invention is excellent in flexibility and oil resistance, hardly discolored by heat, and excellent in moldability.
The molded product of the present invention is excellent in flexibility and oil resistance, hardly discolored by heat, and has few defects due to defective molding.

[Fluororesin composition]
The fluororesin composition of the present invention comprises a melt-kneaded product containing a specific fluorine-containing elastomer and a specific fluororesin. The melt-kneaded product means a product cooled to room temperature after melt-kneading.
The specific fluorine-containing elastomer refers to a “fluorine-containing elastomer having a storage shear modulus G ′ of 100 or more”, and is hereinafter also referred to as “component A”. The specific fluororesin refers to “a melt-moldable fluororesin having a melting point of 150 ° C. or higher”, and is hereinafter also referred to as “component B”.
The fluororesin composition of the present invention is used as a molding material for obtaining a film, a hose, a covered electric wire, and other molded articles.
Hereinafter, the fluororesin composition of the present invention is also referred to as “the present composition”.

  This composition is a melt-kneaded product obtained by melt-kneading raw materials. The raw materials are the specific fluorine-containing elastomer and the specific fluororesin, and it is considered that these raw materials do not change during the melt-kneading process. Therefore, the raw materials before the melt-kneading are also referred to as component A and component B, respectively. In addition, about the C component which is an arbitrary component mentioned later, the raw material changes in a melt-kneading process, and it is thought that the C component in a raw material and a melt-kneaded material differs.

Content of A component with respect to the sum total of A component and B component in this composition is 10-65 mass%. 10-60 mass% is preferable, as for content of the said A component in this composition, 20-60 mass% is more preferable, and 30-55 mass% is further more preferable.
If the A component is contained in the composition within the above range, a molded article having excellent flexibility can be obtained. If the B component is contained in the composition within the above range, a molded article having excellent oil resistance can be obtained.

The total content of the component A and the component B in the composition is 90% by mass or more based on the composition. The total content of the component A and the component B in the composition is preferably 90 to 100% by mass, more preferably 95 to 99.7% by mass, and 97 to 99.5% with respect to the composition. More preferred is mass%.
If the ratio of the total content of the A component and the B component in the mass of the composition is equal to or higher than the lower limit value, the effect of the present invention can be sufficiently exerted. Other components for changing the properties of the product can be included.

  Further, the A component is dispersed in the B component, and the storage elastic modulus E ′ of the present composition at a temperature 25 ° C. higher than the melting point of the B component is 250 kPa or less.

That the A component is dispersed in the B component means that the A component and the B component are phase-separated. Even if the A component and the B component are mixed in the melt-kneading process to form a uniform molten state, it is considered that phase separation occurs in the cooling process. In the case where the A component and the B component are not compatible in the melt-kneading process, the A component is considered to be dispersed as a fine structure in the B-component in the melt-kneading process.
The component A is preferably dispersed in the component B so as to form a sea-island structure (spherical shape) or a co-continuous structure (Gyroid).
In the present invention, the sea-island structure is a discontinuous portion (in the present invention, the A component) in a portion that appears relatively continuous (in the present invention, the B component). It means a structure in a mixed state, and means that the maximum width in each block of discontinuous portions is about 70 μm.
In the present invention, the term “co-continuous structure” means a state in which each lump of discontinuous portions in the sea-island structure has a continuous structure in which a part is joined and continuously connected with a maximum width of 50 μm or less.

The storage elastic modulus E ′ of the present composition was measured for viscoelasticity using the following test piece in an air atmosphere at a frequency of 10 Hz, a temperature rising start temperature: 23 ° C., and a temperature rising temperature: 3 ° C./min. The storage elastic modulus at a temperature 25 ° C. higher than the melting point of the B component.
(Test pieces)
A sheet cut into a length of 45 mm, a width of 8 mm, and a thickness of 1 mm from a 1 mm thick sheet formed by press molding.

The storage elastic modulus E ′ of the composition is 250 kPa or less, preferably 0 to 200 kPa, more preferably 0 to 150 kPa, and still more preferably 0 to 130 kPa.
If the storage elastic modulus E ′ of the present composition is within the above range, sufficient fluidity at the time of molding can be secured, the moldability is excellent, and the molded article containing the composition is excellent in surface smoothness.

(Fluorine-containing elastomer)
In the present invention, the fluorine-containing elastomer as component A exhibits a storage shear modulus G ′ of 100 or more.
The storage shear elastic modulus G ′ of the fluorine-containing elastomer was measured using a Rubber Process Analyzer (RPA2000, manufactured by Alpha Technology Co., Ltd.) according to ASTM D6204, sample amount: 7.5 g, temperature: 100 ° C., displacement: 0.00. G ′ at 50 cpm when the torque is measured by changing the frequency from 1 to 2000 cpm at 5 ° and G ′ and G ″ are calculated from the measured values.

The storage shear modulus G ′ of the fluorine-containing elastomer is 100 or more, preferably from 150 to 1,000, more preferably from 200 to 800, and even more preferably from 220 to 600.
If the storage shear modulus G ′ of the fluorine-containing elastomer is not less than the lower limit, the mechanical strength of the molded article will be good. If the storage shear modulus G ′ is not more than the above upper limit value, it has high fluidity, good dispersion in the component B, and the flexibility of the molded product can be increased.

  The fluorine-containing elastomer as the component A may be an elastic copolymer (elastomer) containing fluorine and having a storage shear modulus G ′ of 100 or more and having no melting point.

The fluorine content in the fluorine-containing elastomer is preferably 50 to 74% by mass or more, and more preferably 55 to 70% by mass or more. Specifically, the fluorine content in the fluorine-containing elastomer is preferably 57 to 60% by mass in the later-described TFE / P-containing copolymer, and 66 to 71% by mass in the later-described HFP / VdF-containing copolymer. Preferably, in the TFE / PMVE-containing copolymer described later, 66 to 70% by mass is preferable.
If the fluorine content in the fluorine-containing elastomer is not less than the lower limit, a molded product having excellent heat resistance and chemical resistance can be obtained. If the fluorine content in the fluorine-containing elastomer is not more than the above upper limit, the flexibility of the molded product can be increased.
The fluorine content of the fluorine-containing elastomer is obtained by analyzing the fluorine content, and indicates the ratio of the mass of fluorine atoms to the total mass of all atoms constituting the fluorine-containing elastomer.

The number average molecular weight of the fluorine-containing elastomer is preferably 10,000 to 1,500,000, more preferably 20,000 to 1,000,000, still more preferably 20,000 to 800,000, and particularly preferably 50,000 to 600,000. When the number average molecular weight of the fluorine-containing elastomer is not less than the lower limit, the mechanical strength of the molded article is good. If the number average molecular weight of the fluorine-containing elastomer is not more than the above upper limit value, it has high fluidity, good dispersion in the component B, and the flexibility of the molded product can be increased.
The number average molecular weight of the fluorine-containing elastomer is a value measured by gel permeation chromatography (hereinafter referred to as “GPC”).

  As component A, one type of fluorine-containing elastomer may be used, or two or more types may be used. As the component A, it is preferable to use one type of fluorine-containing elastomer.

  The fluorine-containing elastomer as component A is one or more monomers selected from tetrafluoroethylene (TFE), hexafluoropropylene (HFP), vinylidene fluoride (VdF), and chlorotrifluoroethylene (CTFE) (hereinafter referred to as “ It is preferably an elastomer containing units based on the monomer (MA1) ”.

  When the fluorine-containing elastomer is an elastomer containing units based on the monomer (MA1), the fluorine-containing elastomer is also a unit based on TFE (hereinafter also referred to as “TFE unit”, the same applies to other units), HFP. It may be an elastomer comprising only two or three units selected from a unit, a VdF unit, and a CTFE unit, and is copolymerizable with the monomer (MA1) and the monomer (MA1). It may be an elastomer composed of one or more units based on another monomer (hereinafter also referred to as “monomer (MA2)”) other than the monomer (MA1) to be a polymer.

  As the monomer (MA2), ethylene, propylene, perfluoro (alkyl vinyl ether) (PAVE), vinyl fluoride (VF), 1,2-difluoroethylene (DiFE), 1,1,2-trifluoroethylene (TrFE) , 3,3,3-trifluoro-1-propylene (TFP), 1,3,3,3-tetrafluoropropylene, and one or more selected from the group consisting of 2,3,3,3-tetrafluoropropylene The compound of this is mentioned. The unit based on ethylene in the polymer is represented by “E”, and the unit based on propylene is represented by “P”.

Here, PAVE is a compound represented by the following formula (I), specifically, perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether). (PPVE) and perfluoro (butyl vinyl ether) (PBVE).
CF ₂ = CF (OR ^F ) (I)
[Wherein, R ^F represents a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms. ]

The fluorine-containing elastomer can be copolymerized with the monomer (MA1), and the other elastomer (hereinafter referred to as “monomer (MA3)”) other than the monomer (MA1) and the monomer (MA2), in which the elastomer becomes an elastic copolymer. May have one or more of the units based on.
Of all the units constituting the fluorine-containing elastomer, the unit based on the monomer (MA3) is preferably 20 mol% or less, more preferably 5 mol% or less, and the unit based on the monomer (MA3). More preferably not.

In the fluorine-containing elastomer, 100 mol% of all units constituting the fluorine-containing elastomer consists of two or three units based on the monomer (MA1), or one or more units based on the monomer (MA1) And one or more units based on the monomer (MA2). However, it is permissible to contain units other than these as impurities, etc., as long as they do not affect the properties of the present composition.
An elastomer comprising two or three units based on the monomer (MA1) and an elastomer comprising one or more units based on the monomer (MA1) and one or more units based on the monomer (MA2) Contributes to flexibility.

The fluorine-containing elastomer as the component A is a TFE / P-containing copolymer (meaning a copolymer containing TFE units and P units. In addition, the total of each unit connected by “/”, TFE / In the case of a P-containing copolymer, the ratio of the total of TFE units and P units to the total of all units is preferably 50 mol% or more, and the same applies to other “containing copolymers”. HFP / VdF-containing copolymers and TFE / PAVE-containing copolymers.
In addition, even if it is a copolymer which has a TFE unit and a PAVE unit, a TFE / PAVE containing copolymer does not contain what further contains a P unit and a VdF unit. Moreover, even if it is a copolymer which has a HFP unit and a VdF unit in a HFP / VdF containing copolymer, what contains a P unit further is not included.

As the TFE / P-containing copolymer, TFE / P (meaning a copolymer composed of TFE units and P units; the same applies to others), TFE / P / VF, TFE / P / VdF, TFE / P / E, TFE / P / TFP, TFE / P / PAVE, TFE / P / 1,3,3,3-tetrafluoropropene, TFE / P / 2,3,3,3-tetrafluoropropene, TFE / P / TrFE, TFE / P / DiFE, TFE / P / VdF / TFP, TFE / P / VdF / PAVE are mentioned, and TFE / P is particularly preferable.
Examples of HFP / VdF-containing copolymers include HFP / VdF, TFE / VdF / HFP, TFE / VdF / HFP / TFP, TFE / VdF / HFP / PAVE, VdF / HFP / TFP, VdF / HFP / PAVE. Of these, HFP / VdF is preferred.
Examples of the TFE / PAVE-containing copolymer include TFE / PAVE, TFE / PMVE, and TFE / PMVE / PPVE. Among them, TFE / PMVE is preferable.

  As the fluorine-containing elastomer, in addition to the above-mentioned TFE / P-containing copolymer, HFP / VdF-containing copolymer, and TFE / PAVE-containing copolymer, TFE / VdF / 2,3,3,3-tetrafluoropropene, VdF / PAVE, VdF / 2,3,3,3-tetrafluoropropene, and E / HFP are also included.

  Among the above fluorine-containing elastomers, a TFE / P-containing copolymer, an HFP / VdF-containing copolymer, and a TFE / PAVE-containing copolymer are preferable, a TFE / P-containing copolymer is more preferable, and a TFE / P copolymer is preferable. More preferred are polymers.

The composition of these elastomers is preferably in the following range from the viewpoint of easily contributing to the flexibility of the molded product obtained from the present composition.
In TFE / P, TFE: P (meaning the molar ratio of TFE units to P units. The units are mol%: mol%, and the total is 100 mol%. The same applies to other molar ratios. ) Is preferably 30 to 80:70 to 20, more preferably 40 to 70:60 to 30, and still more preferably 60 to 50:40 to 50. In TFE / P / VF, TFE: P: VF = 30 to 60:60 to 20: 0.05 to 40, and in TFE / P / VdF, TFE: P: VdF = 30 to 60:60 to 20: 0. 05-40, in TFE / P / E, TFE: P: E = 20-60: 70-30: 0.05-40, in TFE / P / TFP, TFE: P: TFP = 30-60: 60- 30: 0.05-20, in TFE / P / PAVE, TFE: P: PAVE = 40-70: 60-29.95: 0.05-20, TFE / P / 1,3,3,3-tetra In fluoropropene, TFE: P: 1,3,3,3-tetrafluoropropene = 30-60: 60-20: 0.05-40, in TFE / P / 2,3,3,3-tetrafluoropropene , TFE: P: 2, , 3,3-tetrafluoropropene = 30 to 60:60 to 20: 0.05 to 40, and in TFE / P / TrFE, TFE: P: TrFE = 30 to 60:60 to 20: 0.05 to 40, In TFE / P / DiFE, TFE: P: DiFE = 30 to 60:60 to 20: 0.05 to 40, and in TFE / P / VdF / TFP, TFE: P: VdF: TFP = 30 to 60:60 to 20: 0.05 to 40: 0.05 to 20, in TFE / P / VdF / PAVE, TFE: P: VdF: PAVE = 30 to 70:60 to 20: 0.05 to 40: 0.05 to 20 In HFP / VdF, HFP: VdF = 99 to 5: 1 to 95, and in TFE / VdF / HFP, TFE: VdF: HFP = 20 to 40: 1 to 40:20 to 40, TFE / Vd / HFP / TFP, TFE: VdF: HFP: TFP = 30 to 60: 0.05 to 40:60 to 20: 0.05 to 20, TFE / VdF / HFP / PAVE, TFE: VdF: HFP: PAVE = 30 to 70:60 to 20: 0.05 to 40: 0.05 to 20, in VdF / HFP / TFP, VdF: HFP: TFP = 1 to 90:95 to 5: 0.05 to 20, VdF / In HFP / PAVE, VdF: HFP: PAVE = 20 to 90: 9.95 to 70: 0.05 to 20, in TFE / PAVE, TFE: PAVE = 40 to 70:60 to 30, in TFE / PMVE, TFE : PMVE = 40-70: 60-30, TFE: PMVE: PPVE = 40-70: 3-57: 3 in TFE / PMVE / PPVE -57, TFE / VdF / 2,3,3,3-tetrafluoropropene, TFE: VdF: 2,3,3,3-tetrafluoropropene = 1-30: 30-90: 5-60, VdF / In PAVE, VdF: PAVE = 3 to 95:97 to 5, in VdF / 2,3,3,3-tetrafluoropropene, VdF: 2,3,3,3-tetrafluoropropene = 30 to 95:70 to 5. In E / HFP, E: HFP = 40-60: 60-40 is preferable.

(Manufacture of fluorine-containing elastomers)
The fluorine-containing elastomer can be produced by copolymerizing at least one monomer (MA1) and, if necessary, at least one of the monomer (MA2) and the monomer (MA3).
Examples of the polymerization method include an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method. An emulsion polymerization method in which a monomer is polymerized in the presence of an aqueous medium and an emulsifier is preferred because the number average molecular weight and copolymer composition of the fluorinated copolymer can be easily adjusted and the productivity is excellent.
In the emulsion polymerization method, an elastomer latex is obtained through a step (emulsion polymerization step) of polymerizing (emulsion polymerization) a monomer component containing the monomer in the presence of an aqueous medium, an emulsifier and a radical polymerization initiator. In the emulsion polymerization step, a pH adjuster may be added.

(Fluorine resin)
In the present composition, the fluororesin as component B is a melt-moldable resin having a melting point of 150 ° C. or higher.

The fluorine content in the fluororesin as the component B is preferably 50 to 74% by mass, and more preferably 53 to 70% by mass. As another aspect, the fluorine content in the fluororesin is preferably 50 to 70% by mass, and as another aspect, preferably 53 to 74% by mass.
When the fluorine content in the fluororesin is not less than the lower limit value, a molded article having excellent heat resistance and chemical resistance can be obtained. If the fluorine content in the fluororesin is less than or equal to the above upper limit, the flexibility of the molded body can be increased.

The fluorine content of the fluororesin is obtained by analyzing the fluorine content, and indicates the ratio of the mass of fluorine atoms to the total mass of all atoms constituting the fluororesin.
The number average molecular weight of the fluororesin as component B is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, still more preferably 20,000 to 300,000, and even more preferably 50,000 to 300,000. When the number average molecular weight of the fluororesin is not less than the lower limit, the mechanical strength of the molded article is good. If the number average molecular weight of the fluororesin (B) is not more than the above upper limit value, it has high fluidity, can disperse the fluorine-containing elastomer well, and can enhance the flexibility of the molded article.

The melting point of the fluororesin as the component B is 150 ° C. or higher, preferably 150 to 300 ° C., more preferably 160 to 280 ° C., and further preferably 170 to 270 ° C.
If the melting point of the fluororesin is not less than the lower limit, this composition having sufficient heat resistance can be obtained. If the melting point of the fluororesin is not more than the above upper limit value, the present composition and molded product can be produced without requiring a high temperature.

  As a fluororesin which is B component, 1 type may be used and 2 or more types may be used. As the fluororesin, it is preferable to use one kind.

The fluororesin is preferably a polymer containing one or more units based on the following monomer (MB1) to monomer (MB7).
Monomer (MB1): TFE, CTFE.
Monomer (MB2): Compound represented by the following formula (II) (hereinafter also referred to as “FAE”).
CH ₂ = CX (CF ₂ ) _n Y (II)
[Wherein, X and Y are the same or different and each represents a hydrogen atom or a fluorine atom, and n is an integer of 2 to 8.] ]
Monomer (MB3): A fluoroolefin having a hydrogen atom in an unsaturated group such as VdF, vinyl fluoride, trifluoroethylene, hexafluoroisobutylene, or the like.
Monomer (MB4): A fluoroolefin having no hydrogen atom in an unsaturated group such as HFP (excluding the monomer (MB1)).
Monomer (MB5): PAVE.
Monomer _{(MB6): CF 2 = CFOCF} 2 CF = CF 2, CF 2 = CFO (CF 2) a perfluorovinyl ether compound having two unsaturated bonds such as 2 CF = CF _2.
Monomer (MB7): perfluoro (2,2-dimethyl-1,3-dioxole), 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole, perfluoro (2-methylene-4) -Fluorine-containing monomers having an aliphatic ring structure such as methyl-1,3-dioxolane).

From the viewpoint of excellent heat resistance, chemical resistance, weather resistance and non-adhesiveness of the obtained molded product, the fluororesin preferably contains a unit based on the monomer (MB1), and among the units based on the monomer (MB1), More preferably it contains TFE units.
Moreover, from the point which is excellent in the heat resistance of the obtained molded object, chemical resistance, a weather resistance, and non-adhesiveness, a fluororesin is a unit based on a monomer (MB1), and either a monomer (MB2)-a monomer (MB7). It is preferable to include a unit based on one or more kinds of monomers, and a unit based on any one or more of the monomer (MB2), the monomer (MB4), and the monomer (MB5) based on the monomer (MB1). It is more preferable to include a unit based on the monomer (MB1), a unit based on the monomer (MB4), and a unit based on the monomer (MB5).

  In addition, n in Formula (II) is an integer of 2-8, and an integer of 2-6 is preferable from a viewpoint of polymerization reactivity with another monomer, and an integer of 2-4 is more preferable. If n in Formula (II) is more than the said lower limit, generation | occurrence | production of malfunctions, such as a crack generating in resin, can be suppressed. If n in Formula (II) is below the said upper limit, it has favorable polymerization reactivity.

The FAE, _{specifically, CH 2 = CF (CF 2} ) 2 F, CH 2 = CF (CF 2) 3 F, CH 2 = CF (CF 2) 4 F, CH 2 = CF (CF 2) ₅ F, CH ₂ = CF (CF ₂ ) ₈ F, CH ₂ = CF (CF ₂ ) ₂ H, CH ₂ = CF (CF ₂ ) ₃ H, CH ₂ = CF (CF ₂ ) ₄ H, CH ₂ = _{CF (CF 2) 5 H,} CH 2 = CF (CF 2) 8 H, CH 2 = CH (CF 2) 2 F, CH 2 = CH (CF 2) 3 F, CH 2 = CH (CF 2) 4 _{F, CH 2 = CH (CF} 2) 5 F, CH 2 = CH (CF 2) 6 F, CH 2 = CH (CF 2) 8 F, CH 2 = CH (CF 2) 2 H, CH 2 = CH _{(CF 2) 3 H, CH} 2 = CH (CF 2) 4 H, CH 2 = CH (CF 2) 5 H _{CH 2 = CH (CF 2)} 8 H , and the like.

  When the fluororesin contains one or more units based on the monomer (MB1) to the monomer (MB7), the fluororesin can be copolymerized with the monomer (MB1) to the monomer (MB7), the monomer (MB1) to the monomer ( One or more units based on monomers other than MB7) (hereinafter also referred to as “MB8”) may be included.

Examples of the monomer (MB8) include a monomer having no functional group and a functional group-containing monomer.
As a monomer which does not have a functional group, the following monomer is mentioned, for example.
α-olefins: ethylene, propylene, butene and the like.
Alkyl vinyl ethers: ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and the like.
Vinyl esters: vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate, myristic acid Vinyl, vinyl palmitate, vinyl stearate, vinyl benzoate, vinyl para-t-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotrate, sorbic acid Vinyl, vinyl cinnamate, vinyl undecylenate, vinyl hydroxyacetate, vinyl hydroxypropioate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxyisobutyrate, vinyl hydroxycyclohexanecarboxylate, etc.
Alkyl allyl ethers: ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, cyclohexyl allyl ether, and the like.
Alkyl allyl esters: ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, cyclohexyl allyl ester, and the like.
Examples of the functional group-containing monomer include the following monomers.
Vinyl ethers having a hydroxyl group and an epoxy group: glycidyl methacrylate and the like.
Unsaturated carboxylic acid: acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, undecylenic acid and the like.
Unsaturated carboxylic anhydrides: maleic anhydride, itaconic anhydride, citraconic anhydride, hymic anhydride, and the like.

Examples of the fluororesin as component B include TFE-containing polymers (meaning polymers having TFE units. The same applies to other “containing polymers”), VdF-containing polymers, and CTFE-containing polymers. .
A polymer having VdF units is a VdF-containing polymer even if it has TFE units or CTFE units. In addition, the CTFE-containing polymer does not include a polymer having CTFE units, which further includes one or both of TFE units and VdF units.

Examples of the TFE-containing polymer include an E / TFE-containing copolymer, a TFE / HFP-containing copolymer, and a TFE / PAVE-containing copolymer.
Examples of the CTFE-containing polymer include E / CTFE-containing copolymers.
Moreover, PFA is mentioned as 1 type of a TFE / PAVE containing copolymer.

  The B component is a melt-moldable fluororesin having a melting point of 150 ° C. or higher, and the A component is an elastic copolymer having no melting point. Therefore, for example, the TFE / PAVE-containing copolymer as the B component is different from the TFE / PAVE-containing copolymer as the containing A component.

  Among the above fluororesins, the following ETFE and E / CTFE-containing copolymers are preferable as the B component from the viewpoint of excellent balance of heat resistance, chemical resistance, and mechanical strength. As an embodiment, the following ETFE is more preferable. Preferably, as another embodiment, an E / CTFE-containing copolymer is more preferable.

The E / TFE-containing copolymer has a molar ratio of E units: TFE units of 80:20 to 20:20 because it tends to contribute to an excellent balance of heat resistance, chemical resistance and mechanical strength of the composition. E / TFE-containing copolymer (hereinafter referred to as “ETFE”), which is 80 and includes units other than E units and TFE units (hereinafter also referred to as “third units”) in an amount of 20 mol or less relative to all units. Say). The molar ratio of E unit to TFE unit in ETFE is more preferably 70:30 to 30:70, and further preferably 50:50 to 35:65.
The content of the third unit in ETFE is preferably 0.01 to 20 mol%, more preferably 0.1 to 10 mol%, and still more preferably 0.8 to 5 mol% with respect to all units.
As the third unit, a unit based on FAE is preferable.

When ETFE is used as the component B, ETFE having a melting point of 150 to 300 ° C is preferable, ETFE having a melting point of 160 to 280 ° C is more preferable, and ETFE having a melting point of 170 to 270 ° C is more preferable.
As the ETFE in the case of using ETFE as the B component is preferably ETFE having a volume flow rate of 0.1~200mm ³ / sec, more preferably ETFE having a volume flow rate of 0.5 to 100 mm ³ / sec, 1 More preferred is ETFE having a volumetric flow rate of ˜50 mm ³ / sec.
The volume flow rate is an index representing the melt fluidity of the resin and is a measure of the molecular weight. A large volumetric flow rate indicates a low molecular weight, and a small volumetric flow rate indicates a high molecular weight.
The flow rate of the resin is the extrusion speed of the resin when extruded into an orifice with a diameter of 2.1 mm and a length of 8 mm under a load of 7 kg at a temperature 50 ° C. higher than the melting point of the resin using a flow tester manufactured by Shimadzu Corporation. As obtained.

(Other ingredients)
In addition to the A component and the B component, the present composition may contain other components as optional components. However, it does not include a component having an action such as modifying the A component or the B component during melt-kneading (for example, a crosslinking agent or a crosslinking aid described later).
Examples of the other components include an ethylene copolymer derived from an ethylene copolymer containing an epoxy group and a flame retardant, and one or both of them may be contained in the composition. .
The “ethylene copolymer derived from an ethylene copolymer containing an epoxy group” is hereinafter also referred to as “C component”.

  The sum total of the said other component which occupies for this composition is 10 mass% or less of this composition, 8 mass% or less is preferable, and 5 mass% or less is more preferable.

  The present composition may contain an ethylene copolymer which is a C component in addition to the A component and the B component. The C component can increase the compatibility between the A component and the B component, and can improve the dispersion of the A component in the B component.

Component C is a component contained in the fluororesin composition that is a melt-kneaded product, and is derived from an ethylene copolymer that contains an epoxy group before melt-kneading. When an ethylene copolymer containing an epoxy group is melt-kneaded together with the fluorine-containing elastomer or the fluorine-containing resin to obtain a melt-kneaded product, part or all of the epoxy group is considered to be lost due to the reaction. The disappearance of the epoxy group during melt-kneading is presumed to contribute to the action of the C component increasing the compatibility between the A component and the B component and improving the dispersibility of the A component.
The content of component C in the melt-kneaded product contains epoxy groups in all raw material components (composed of an ethylene copolymer containing component A, component B and an epoxy group, and optionally a flame retardant) prior to melt-kneading. It is equal to the content of ethylene copolymer. This is because even if the epoxy group disappears, the mass change between the proportion of the ethylene copolymer containing the epoxy group in the raw material and the C component in the present composition can be ignored.

When this composition contains C component, content of C component is 0.1-10 mass parts with respect to a total of 100 mass parts of A component and B component, and 0.3-8 mass parts is Preferably, 0.5-5 mass parts is more preferable.
If the content of component C is not less than the lower limit, it is difficult to cause thermal discoloration of the composition or the molded article, and if it is not more than the upper limit, a molded article having sufficient oil resistance and heat resistance can be obtained.

<Ethylene copolymer containing epoxy group>
The ethylene copolymer containing an epoxy group has a melting point capable of being melt-kneaded together with the fluorine-containing elastomer or the fluorine-containing resin. That is, its melting point is less than 150 ° C.

  As an ethylene copolymer containing an epoxy group, 1 type may be used and 2 or more types may be used. As the ethylene copolymer containing an epoxy group, it is preferable to use one kind.

  As an ethylene copolymer containing an epoxy group, a binary or higher copolymer consisting of an E unit and a unit based on one or more monomers having an epoxy group (hereinafter also referred to as “monomer (MC1)”). 1 unit of monomer, other than ethylene and monomer (MC1) (hereinafter also referred to as “monomer (MC2)”) copolymerizable with ethylene, a unit based on one or more types of monomer (MC1), and ethylene. An ethylene copolymer such as a ternary or higher copolymer composed of units based on species or more may be mentioned.

Examples of the monomer (MC1) include unsaturated glycidyl ethers (such as allyl glycidyl ether, 2-methylallyl glycidyl ether, and vinyl glycidyl ether), and unsaturated glycidyl esters (such as glycidyl acrylate and glycidyl methacrylate).
As the monomer (MC1), glycidyl methacrylate is preferable from the viewpoint of improving the compatibility between the A component and the B component.

As monomers (MC2), acrylic esters (methyl acrylate, ethyl acrylate, etc.), methacrylic esters (methyl methacrylate, ethyl methacrylate, etc.), fatty acid vinyl esters (vinyl acetate, etc.), other than ethylene Examples include α-olefins.
From the viewpoint of improving the compatibility between the A component and the B component, the monomer (MC2) includes acrylic acid esters, methacrylic acid esters, and fatty acid vinyl esters (hereinafter collectively referred to as “monomer (MC3)”). The monomer (MC3) is a partial assembly of the monomer (MC2).

As an ethylene copolymer containing an epoxy group, E / methacrylic acid having an E unit and a glycidyl methacrylate unit, from the viewpoint of more excellent properties such as moldability of the composition, flexibility of the molded product, and oil resistance. A glycidyl acid-containing copolymer is preferable, and an E / glycidyl methacrylate copolymer and an E / glycidyl methacrylate / monomer (MC3) copolymer are more preferable.
E / glycidyl methacrylate / monomer (MC3) copolymer includes E / glycidyl methacrylate / vinyl acetate copolymer, E / glycidyl methacrylate / methyl acrylate copolymer, E / glycidyl methacrylate / ethyl acrylate. Examples of the copolymer include E / glycidyl methacrylate / methyl acrylate copolymer and E / glycidyl methacrylate / ethyl acrylate copolymer.

The content of E units in the ethylene copolymer containing an epoxy group is preferably 55 to 99.9 mol%, more preferably 70 to 94 mol%, from the viewpoint of heat resistance and toughness of the molded body.
The content of units based on the monomer (MC1) in the ethylene copolymer containing an epoxy group is preferably 0.1 to 45 mol% from the viewpoint of moldability of the composition and mechanical properties of the molded body. 1-10 mol% is more preferable.
When the ethylene copolymer containing an epoxy group has a unit based on the monomer (MC2), the content of the unit based on the monomer (MC2) in the ethylene copolymer containing the epoxy group is 1 to 30 mol%. Is preferable, and 5 to 20 mol% is more preferable.

  When an ethylene copolymer containing an epoxy group having a content of each unit within the above range is used, the compatibility between the component A and the component B can be further improved. As a result, the moldability of the present composition is excellent, and the resulting molded product is more excellent in properties such as flexibility, oil resistance, and heat resistance.

  A commercially available product can also be used as the ethylene copolymer containing an epoxy group, and as a commercially available product of an ethylene copolymer containing an epoxy group, “bond first (registered trademark) E” (manufactured by Sumitomo Chemical Co., Ltd., E / glycidyl methacrylate copolymer) and “bond first 7M” (manufactured by Sumitomo Chemical Co., Ltd., E / glycidyl methacrylate / methyl acrylate copolymer).

<Flame Retardant>
It does not specifically limit as a flame retardant, A well-known flame retardant can be employ | adopted.
Flame retardants include aluminum hydroxide, magnesium hydroxide, magnesium carbonate, antimony trioxide, sodium antimonate, antimony pentoxide, phosphazene compounds, phosphate esters, ammonium polyphosphate, melamine, melam, melem, polyphosphoric acid, red phosphorus, A molybdenum compound, a boric acid compound, PTFE, etc. are mentioned. Among them, antimony trioxide, aromatic phosphate ester (triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc.), PTFE (forms a fibril structure in the resin) Anti-drip agent) is preferred.

(Method for producing fluororesin composition)
The fluororesin composition of the present invention is produced by melting and kneading and cooling the A component, the B component, and optionally the optional component. The cooled melt-kneaded product is preferably a solid melt-kneaded product used as a molding material, formed into pellets or granules of an appropriate size. As the melt kneading method, a method of melt kneading extrusion with an apparatus having a melt kneading extrusion mechanism is preferable. The melt-kneaded and extruded linear melt-kneaded product can be cut into an appropriate size to form a pellet-like or granular melt-kneaded product.
The optional component is melt-kneaded together with the components when the component A and the component B are melt-kneaded and extruded.
As described above, the optional component C is a component derived from an ethylene copolymer having an epoxy group as a raw material. An ethylene copolymer having an epoxy group becomes a C component by melt-kneading, but it is considered that there is no quantitative change of the substance in the change (disappearance of epoxy group), and therefore has an epoxy group in the raw material before melt-kneading. The amount of the ethylene copolymer is 0 to 10 parts by mass with respect to a total of 100 parts by mass of the specific fluorine-containing elastomer and the specific fluororesin.

As an apparatus used for melt-kneading extrusion, it is preferable to use an apparatus having a melt-kneading extrusion mechanism of two or more axes such as a twin-screw extruder and a multi-screw extruder, a twin-screw extruder equipped with a screw having a high kneading effect, kneading It is more preferable to use a multi-screw extruder equipped with a highly effective screw.
As the screw having a high kneading effect, a screw that gives a sufficient kneading effect to the melt-kneaded extrusion target and does not give an excessive shearing force can be selected.

The apparatus having a biaxial or higher melt kneading extrusion mechanism is preferably an apparatus having a continuous biaxial or higher melt kneading extrusion mechanism.
By using an apparatus having a continuous biaxial or higher melt kneading extrusion mechanism, a sufficient kneading effect can be given to the melt kneading extrusion target. When an apparatus having a batch-type melt-kneading / extrusion mechanism is used, a shearing force is insufficient, so that a sufficient kneading effect may not be given to an object to be melt-kneaded / extruded.

Moreover, it is preferable that the apparatus which has a biaxial or more melt kneading extrusion mechanism is equipped with one or more kneading zones, and is equipped with two or more kneading zones.
Further, the length L of the kneading zone with respect to the screw diameter D in the apparatus having the melt kneading and extruding mechanism of two or more axes (when two or more kneading zones are provided, the total length of the respective kneading zones) The ratio (L / D) is preferably from 0.1 to 50, more preferably from 1 to 20, and even more preferably from 3 to 10.

  The kneading temperature in the melt-kneading extrusion is preferably 5 ° C. or more higher than the melting point of the component B, more preferably 5 to 80 ° C., more preferably 5 to 50 ° C. .

The shear rate in the melt-kneading extrusion is preferably set according to the melt viscosity of the melt-kneading extrusion target at the kneading temperature in the melt-kneading extrusion.
50-700 rpm is preferable, as for the rotation speed of the screw of the apparatus which has the melt kneading extrusion mechanism of 2 or more axes in melt-kneading extrusion, 100-500 rpm is more preferable, 200-400 rpm is more preferable.

  By appropriately adjusting the number of kneading zones, kneading zone length, kneading temperature, and shear rate in melt-kneading extrusion, the storage modulus of the composition at a temperature 25 ° C. higher than the melting point of the component B E ′ can be controlled to 250 kPa or less.

By providing more kneading zones, the component A dispersed in the component B can be made smaller in the melt-kneading extrusion, and a better dispersion state can be obtained.
Further, by setting the length of the longer kneading zone (the sum of the lengths of the respective kneading zones when two or more kneading zones are provided), the components are dispersed in the B component in the melt-kneading extrusion. The component A can be made smaller in particle size and can be in a better dispersion state.
Further, by setting the kneading temperature to a higher value, the component A dispersed in the component B can be made smaller in the kneading and extrusion so as to have a better dispersion state.
Moreover, by setting it as a larger shear rate, in extrusion kneading | mixing, the A component disperse | distributed in B component can be made smaller particle size, and it can be set as a more favorable dispersion state.

  By appropriately adjusting these conditions, in melt-kneading extrusion, by sufficiently reducing the particle size of the A component dispersed in the B component and making it a sufficiently dispersed state, at a temperature 25 ° C. higher than the melting point of the B component, The storage elastic modulus E ′ of the present composition can be controlled to 250 kPa or less.

The melt-kneading extrusion is performed until the viscosity of the melt-kneaded extrusion object becomes constant. The viscosity change during the melt-kneading extrusion of the melt-kneaded extrusion object can be observed by the change with time of the rotational torque by a torque meter via a screw.
“Until the viscosity of the melt-kneaded extrudate becomes constant” means that the melt-kneaded extrusion is performed until the fluctuation of the rotational torque value is within 5% of the center value for a certain time or more.
The time required for melt-kneading extrusion may vary depending on the kneading temperature, shear rate, composition of the melt-kneaded extrusion target object, screw shape of an apparatus having a biaxial or higher melt-kneading extrusion mechanism, etc., from the viewpoint of economy and productivity 1 to 30 minutes are preferable, 1 to 20 minutes are more preferable, and 2 to 10 minutes are more preferable.

As a form of A component used for melt-kneading extrusion, a crumb is preferable. In particular, it is preferable to dry and use the crumb of the fluorine-containing elastomer obtained by agglomerating the latex of the elastomer obtained by emulsion polymerization.
As a form of B component used for melt-kneading extrusion, a powder is preferable. As the powder, those having a small particle diameter are more preferable. When the particle size is small, kneading in melt-kneading extrusion becomes easy, and a uniform melt-kneading extrusion state is easily obtained. In particular, the powder is preferably a fluororesin powder obtained by drying a resin slurry obtained by solution polymerization.
Further, before carrying out the melt-kneading extrusion, the A component crumb and the B component powder may be mixed without heating using a known apparatus. In addition, the A component crumb and the B component powder may be mixed in an apparatus having a biaxial or higher melt kneading extrusion mechanism at the time of melt kneading extrusion.

[Molding materials]
The molding material of the present invention is a molding material containing the present composition. Hereinafter, the molding material containing the composition is also referred to as “main molding material”.
The present molding material made of the present composition is a molding material in the form of pellets, granules, powders, etc. The present molding material containing the following compounding agent has the present composition having a shape of pellets, granules, powders, etc. It is preferable that it is a mixture of a product and a compounding agent. In some cases, in the case of a molding material containing a compounding agent other than the compounding agent that reacts with the components in the composition such as a crosslinking agent, the composition and the compounding agent are melt-mixed to form pellets, granules, powders, etc. It may be a molding material having the following shape.
Since the present molding material has a melt viscosity lower than that of the component A contained in the present composition, the take-up speed can be set large, so that the molding processability is excellent.
In addition to the present composition, this molding material is a cross-linking agent, a crosslinking aid, a filler, a stabilizer, a colorant, an antioxidant, a processing aid, a lubricant, and a lubrication depending on the intended use of the molded product. 1 type or more of compounding agents, such as an agent and an antistatic agent, may be contained. When manufacturing the crosslinked molded object, it is preferable to contain a crosslinking agent or a crosslinking adjuvant among these compounding agents.

Any conventionally known crosslinking agent can be used as the crosslinking agent, but organic peroxides are preferred. Any organic peroxide can be used as long as it easily generates radicals in the presence of heating and redox. This composition crosslinked with an organic peroxide is excellent in heat resistance.
Specific examples of the organic peroxide include 1,1-di (t-hexylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, Di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (T-butylperoxy) -hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3, dibenzoyl peroxide, t-butylperoxybenzene, 2,5 -Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-hexylperoxyisopropyl monocarbonate and the like. Among them, α, α′-bis (t-butylperoxy) -p-diisopropylbenzene is exemplified. These organic peroxides are excellent in the crosslinkability of the fluorine-containing elastomer composition.
When manufacturing the crosslinked molded object, 0.1-5 mass parts is preferable with respect to 100 mass parts of A component, and, as for content of the crosslinking agent in this molding material, 0.2-4 mass parts is more. Preferably, 0.5-3 mass parts is more preferable. When the content of the crosslinking agent is within the above range, the crosslinking efficiency of the organic peroxide is high.
One or more crosslinking agents can be used.

Examples of the crosslinking aid include triallyl cyanurate, triallyl isocyanurate, triacryl formal, triallyl trimellitate, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, among others. Triallyl isocyanurate is preferred.
When manufacturing the crosslinked molded object, 0.1-30 mass parts is preferable with respect to 100 mass parts of A component, and, as for content of the crosslinking adjuvant in this molding material, 0.5-15 mass parts is More preferred is 1 to 10 parts by mass. When the content of the crosslinking aid is not less than the lower limit, the crosslinking rate is high and a sufficient degree of crosslinking is easily obtained. If content of a crosslinking adjuvant is below the said upper limit, characteristics, such as elongation of a crosslinked material, will become favorable.
One or more crosslinking aids can be used.

Examples of the filler include carbon black, white carbon, clay, talc, calcium carbonate, glass fiber, carbon fiber, fluororesin (polytetrafluoroethylene, ETFE, etc.) and the like.
Any carbon black can be used without limitation as long as it is used as a filler for fluororubber. Specific examples thereof include furnace black, acetylene black, thermal black, channel black, and graphite, and furnace black is preferable. Examples of furnace black include HAF-LS carbon, HAF carbon, HAF-HS carbon, FEF carbon, GPF carbon, APF carbon, SRF-LM carbon, SRF-HM carbon, MT carbon, and among these, MT carbon Is more preferable.
When this molding material contains carbon black, 1-50 mass parts is preferable with respect to 100 mass parts of A component, and 3-20 mass parts is more preferable. If the content of carbon black is not less than the lower limit, the strength of the molded article is excellent, and the reinforcing effect due to the incorporation of carbon black can be sufficiently obtained. Further, if the carbon black content is not more than the above upper limit value, the elongation of the molded article is also excellent. As described above, when the carbon black content is within the above range, the balance between the strength and elongation of the molded article is good.

When this molding material contains fillers other than carbon black, 5-200 mass parts is preferable with respect to 100 mass parts of this composition, and 10-100 mass parts is more preferable.
One or more fillers can be used, and carbon black and other fillers may be used in combination. When this molding material contains carbon black and other fillers, the content thereof is preferably 1 to 100 parts by mass and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the present composition. preferable.

Examples of the stabilizer include copper iodide, lead oxide, calcium oxide, magnesium oxide, aluminum oxide, titanium oxide, antimony oxide, and phosphorus pentoxide. The content of the stabilizer in the molding material is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and 0.5 to 3 parts by mass with respect to 100 parts by mass of the composition. Is more preferable. One or more stabilizers can be used.
Examples of the processing aid include higher fatty acids and alkali metal salts of higher fatty acids. Specifically, stearic acid, stearates and laurates are preferred. 0.1-10 mass parts is preferable with respect to 100 mass parts of this composition, as for content of the processing aid in this molding material, 0.2-5 mass parts is more preferable, and 1-3 mass parts is. Further preferred. One or more processing aids can be used.
Examples of the lubricant include higher fatty acids and alkali metal salts of higher fatty acids. Specifically, stearic acid, stearates and laurates are preferable. 0.1-20 mass parts is preferable with respect to 100 mass parts of this composition, as for content of a lubricant, 0.2-10 mass parts is more preferable, and 1-5 mass parts is more preferable.

[Molded body]
The molded body of the present invention is a molded body obtained by melt molding the present molding material. The molded body of the present invention may be a molded body obtained by crosslinking the molding material during melt molding, or a molded body obtained by crosslinking a molded body obtained by melt molding the molding material after molding. It may be. Hereinafter, a molded body obtained by melt molding the present molding material is also referred to as a “main molded body”.

  Examples of the melt molding method for producing the present molded body include injection molding, extrusion molding, coextrusion molding, blow molding, compression molding, inflation molding, transfer molding, and calendar molding.

  There is no particular limitation on the crosslinking method for producing the molded article comprising the crosslinked product, and a chemical crosslinking method, X-ray, γ-ray, electron beam, proton beam, deuteron using the molding material containing the crosslinking agent is used. Examples thereof include an irradiation crosslinking method using ionizing radiation such as rays, α rays, and β rays, and crosslinking may be performed simultaneously with molding, or crosslinking may be performed after molding.

The shape of the molded body is not particularly limited, and may be a film or sheet shape, a hollow hose shape or a tube shape, and various other shapes depending on applications.
The molded body may be an independent molded product itself, or may be associated with another member such as a covering material.
The molded body is a molded body composed of a single-layer or multi-layered film, sheet, hose or tube, and at least one of the layers in the molded body is a layer formed by melt-molding the molding material. Certain molded bodies are preferred. Further, a covered electric wire having a conductive wire and a covering material, which is a covering material formed by melt-molding the molding material, is preferable.

[Film or sheet]
Specific uses of the film-shaped or sheet-shaped main molded body include mold release applications and agricultural applications. The film or sheet may be a single layer or a laminate of two or more layers. In the case of a laminated body, at least one layer is a layer that is a molded body of the present molding material, and may include a layer formed of a material other than the present molding material.
The use of the film or sheet is not particularly limited. For example, the following uses are mentioned.
Semiconductor release film, substrate release film, release film for optical element sealing process such as light emitting diode (LED), anticorrosion lining, release lining, anticorrosion coating, release coating, wire coating, carbon or glass fiber composite molding Mold release film, copy roll, antifouling film for office equipment such as copy belt, flameproof membrane material, green sheet and fuel cell electrode, carrier film for membrane production, cushion film for high heat press (cushion film for die attach etc. ), Solar cell surface protective film, solar cell back sheet constituent material, carrier film for various sheet members (green sheet, silicon film, etc.), rubber plug laminated film, fire fighting laminate film, display surface protective sheet material, film structure Architectural membrane materials, agricultural houses, chemicals Tsu grayed, exterior materials of lithium ion battery (LIB), construction materials for PVC laminate or wallpaper, steel laminates, insulation (motor insulation), and the like. The green sheet refers to an unsintered ceramic sheet for a ceramic capacitor.
Since the film or sheet as the molded article is excellent in flexibility, it is particularly suitable for use as a semiconductor release film, a release film for sealing an optical element such as an LED, and a laminated film for a rubber plug. The film or sheet may be a single layer or a laminate of two or more layers.

[Coated wire]
In the covered electric wire having the covering material which is the formed body, the covering material formed on the outer periphery of the core wire is not only formed in direct contact with the core wire but also indirectly through another layer between the core wire. It may be formed on the outer periphery. Specifically, the coated electric wire of the present invention is not only coated with a conductor using the molded body of the present invention as a covering material, but also an electric wire having the molded body as a coating material as an outer layer, such as a cable or a wire harness having a sheath. Such things are also included. Examples of the molded body include the film.
The conductor is not particularly limited, and examples thereof include copper, copper alloy, aluminum and aluminum alloy, various plating wires such as tin plating, silver plating, and nickel plating, stranded wires, superconductors, and plating wires for semiconductor element leads.
The covered electric wire which coat | covered the conductor by using the molded object of this invention as a coating | covering material can be manufactured by coat | covering a conductor with this molding material. The conductor can be coated with the molding material by a known method.
The covered electric wire with the formed body as a covering material is coated with the formed body which is a cross-linked product obtained by further irradiating an electron beam onto the covered electric wire whose conductor is coated with the forming material and crosslinking the formed body. It is good also as the covered electric wire used as the material.
The irradiation dose of the electron beam at the time of crosslinking is preferably 50 to 700 kGy, more preferably 80 kGy to 400 kGy, and still more preferably 100 to 250 kGy. 0-300 degreeC is preferable, as for the temperature at the time of irradiation of an electron beam, 10-200 degreeC is more preferable, and 20-100 degreeC is further more preferable.
Since this molding material is excellent in molding processability, a covered electric wire can be manufactured at high speed. In addition, since it contains the A component, it can be used continuously at high temperatures and has excellent flexibility compared to a covered electric wire using only the B component that is thermoplastic as a covering material. It is suitable for use in a coated electric wire for automobiles that needs to be wired. The covering material may be a single layer or a laminate of two or more layers.

[Hose or tube]
The hose or tube which is the main molded body may be a multilayer structure having a layer of the main molded body and a layer made of another material. Examples of other materials include those described in paragraph [0040] of International Publication No. 2015/182702, liquid crystal polymers, polyaryl ketones, polyether sulfones, polyphenyl sulfones, polyacetals, polyurethanes, and the like. Of these, polyamide is preferred.
As polyamides, polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66 copolymer, polyamide 6/66/610 copolymer, polyamide MXD6, polyamide 6T, polyamide 9T and polyamide 6 / 6T copolymer and those described in paragraphs [0051] and [0052] of Japanese Patent No. 4619650.
For the structure and manufacturing method of the laminated hose, refer to the paragraph [0053] to [0063] of the Japanese Patent No. 4619650 by substituting the “inner layer (I) comprising a fluorinated copolymer” with the molded article of the present invention. Can do.
Moreover, you may have another layer between the layer of polyamide and the layer of this molded object. Examples of the other layer include a component B having a functional group-containing monomer as the monomer (MB8) because of good adhesion. Specifically, the fluoropolymer described in International Publication No. 2015/182702 is mentioned.

The use of the hose or tube is not particularly limited. For example, the following uses are mentioned.
Automotive hoses such as fuel hoses, intake / exhaust hoses, various oil hoses including transmission hoses such as ATF hoses, parts tubes, etc., except for automobiles, chemical tubes, chemical hoses, steam tubes, steam hoses There are no particular restrictions on chemical tubes such as gas-liquid tubes, various tubes and hoses in food plants and food equipment, and general industrial parts. In the case of a tube having a thickness of 1 mm, an outer diameter of 8 mm, and an inner diameter of 6 mm, the minimum bending radius of the tube is preferably 42 mm or less, more preferably 40 mm or less, and most preferably 38 mm or less.
Since this molding material is excellent in molding processability, hoses and tubes can be manufactured at high speed. Moreover, since the hose and tube which are this molded object are excellent also in a softness | flexibility, it is suitable for the use for the automotive use etc. which need piping for space saving.
The hose and tube may be a single layer or a laminate of two or more layers.

In addition to the above uses, the molded body can be used as an electrical insulating material for electrical parts, for example, sheathing materials and insulation coating materials for cables. Gaskets in various plants such as petroleum refining, petrochemical, electric power, and papermaking It can also be used as a packing, a diaphragm or the like. Moreover, it can also be set as the various components used in various industrial fields, such as a motor vehicle field, an industrial robot field, and a thermal equipment field.
Among them, it is suitable for various seals, rings, gaskets, packings, joint sheets, pump seals, oil seals, diaphragms and other sealing applications, insulation materials, sheaths and other electric wire / electric equipment related materials. In addition, it is suitable for anti-vibration materials, rolls, scrapers, valve parts, pump parts, mandrels, joints, resin plates, covers, paints, chemical stoppers, piping, sanitary packing, joints, and the like.

(Mechanism of action)
The inventors have found that when the present composition is molded, a good molded article excellent in surface smoothness can be obtained not only in static molding such as press molding but also in dynamic molding such as extrusion molding. I found out. On the other hand, in the conventional fluororesin composition, a molded body having good characteristics can be obtained in static molding such as press molding, while the characteristics are maintained in dynamic molding such as extrusion molding. It has been found that molding defects may occur, such as insufficient surface smoothness.
In order to clarify the cause of this difference, characteristics of each fluororesin composition were evaluated, and it was found that a difference was observed in the storage elastic modulus E ′ in the fluororesin composition.

The storage elastic modulus E ′ of the fluororesin composition is considered to be an index indicating the dispersibility of the fluoroelastomer in the fluororesin composition.
That is, when the fluoroelastomer is not sufficiently dispersed in the fluororesin, even if the temperature exceeds the melting point of the fluororesin, sufficient fluidity cannot be obtained due to the influence of the continuous phase of the fluoroelastomer. The storage elastic modulus E ′ of the object is increased.
On the other hand, when the fluorine-containing elastomer is sufficiently reduced in particle size and dispersed in the fluororesin, if the fluororesin melts at a temperature higher than the melting point of the fluororesin, the fluidity of the entire fluororesin composition increases. The storage elastic modulus E ′ of the fluororesin composition becomes small.

The following can be considered as causes of problems in dynamic molding when the storage elastic modulus E ′ of the fluororesin composition is large. That is, the fluororesin composition having a large storage elastic modulus E ′ at first glance seems to have a sufficient particle size of the fluoroelastomer in the present composition even though the fluoroelastomer appears to be sufficiently dispersed in the fluororesin. It is thought that it is larger than the particle size of. For this reason, it was considered that the dispersed state cannot be maintained by agglomeration of fluorine-containing elastomers having low compatibility with the fluororesin during dynamic molding. That is, when the fluorine-containing elastomer is sufficiently reduced in particle size and not dispersed, the dispersion of the fluorine-containing elastomer is in a non-equilibrium state, and phase separation due to spinodal decomposition proceeds especially in dynamic molding. It was.
Therefore, in the conventional fluororesin composition, a molded body having good characteristics is obtained in static molding such as press molding, while in the dynamic molding such as extrusion molding, the dispersed fluorine-containing elastomer is used. Even if it is a fluororesin composition that aggregates due to phase separation by spinodal decomposition and shows good physical properties before molding, the physical properties change by dynamic molding, and good physical properties before molding It was speculated that could not be held.

  On the other hand, in this composition, since the fluorine-containing elastomer in the fluororesin composition is sufficiently reduced in particle size and dispersed, the storage elastic modulus E ′ of the fluororesin composition is as small as 250 kPa or less. It is considered a thing. Further, since the fluorine-containing elastomer in the fluororesin composition is sufficiently reduced in particle size and dispersed, the progress of phase separation due to spinodal decomposition is suppressed, and the molding material containing the fluororesin composition is dynamically changed. Even when molded, it is considered that a good molded article having excellent surface smoothness can be obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
The materials used in each example are shown below.

<Fluorine-containing elastomer>
A1: Fluorine-containing elastomer (TFE / P copolymer (Mole ratio of TFE unit / P unit = 56/44, fluorine content = 57% by mass, Mooney viscosity (ML _{1 + 10} (121 ° C. )) = 120, glass transition temperature (Tg) = − 3 ° C., storage shear modulus G ′ = 530)).
The inside of a 3.2 L reactor equipped with a stirring anchor blade was evacuated, and 1500 g of ion-exchange water, 59 g of disodium hydrogen phosphate dodecahydrate, 0.7 g of sodium hydroxide, and tert-butanol 197 g, 9 g of sodium lauryl sulfate, and 6 g of ammonium persulfate were added. Further, an aqueous solution in which 0.4 g of ethylenediaminetetraacetic acid disodium salt dihydrate and 0.3 g of ferrous sulfate heptahydrate were dissolved in 100 g of ion exchange water was added to the reactor. At this time, the pH of the aqueous medium in the reactor was 9.5.
Next, a monomer mixed gas of TFE / propylene = 88/12 (molar ratio) was injected at 25 ° C. so that the internal pressure of the reactor was 2.50 MPaG. The anchor blade was rotated at 300 rpm, and then a 2.5% by mass aqueous solution of sodium hydroxymethanesulfinate dihydrate adjusted to pH 10.0 with sodium hydroxide (hereinafter, “Longalite 2.5% by mass aqueous solution”) Was added to the reactor to initiate the polymerization reaction. Thereafter, Rongalite 2.5 mass% aqueous solution was continuously added to the reactor using a high-pressure pump. When the total amount of the TFE / propylene monomer mixed gas injected reaches 1000 g, the addition of the 2.5% by weight aqueous solution of Rongalite is stopped, the internal temperature of the reactor is cooled to 10 ° C., and the polymerization reaction is performed. It stopped and the latex of the fluorine-containing elastomer was obtained. The amount of Rongalite 2.5 mass% aqueous solution added was 68 g. The polymerization time was 6 hours. A 5% by mass aqueous solution of calcium chloride was added to the latex to agglomerate the latex of the fluorine-containing elastomer A1, and the fluorine-containing elastomer was precipitated, filtered and collected.

A2: Fluorinated elastomer (TFE / P copolymer (Mole ratio of TFE unit / P unit = 56 /) produced in the same manner as the production method of A1 except that the polymerization temperature was changed from 25 ° C. to 40 ° C. 44, fluorine content: 57 mass%, Mooney viscosity (ML _{1 + 10} (121 ° C.)) = 100, glass transition temperature (Tg) = − 3 ° C., storage shear modulus G ′ = 390)).

<Fluorine resin>
B1: Fluororesin (ethylene / TFE / (perfluorobutyl) ethylene copolymer (E unit / TFE unit / (perfluorobutyl) methylene unit molar ratio = 40 / 57/3, melt flow rate (MFR) = 25 g / 10 min, Tg = 75 ° C., Tm = 225 ° C.)).

B2: Fluororesin (ethylene / TFE / (perfluorobutyl) ethylene copolymer (E unit / TFE unit / (perfluorobutyl) methylene unit molar ratio) produced in the same manner as in Production Example 2 of WO2016 / 002887 = 46 0.0 / 54.0 / 1.50, melt flow rate (MFR) = 11.3 g / 10 min, Tg: 240 ° C., Tm = 255 ° C.)).

<Ethylene copolymer containing epoxy group>
C1: “Bond First (registered trademark) 7M” (E / glycidyl methacrylate / methyl acrylate copolymer, manufactured by Sumitomo Chemical Co., Ltd.).

<Measurement of storage shear modulus G '>
The storage shear elastic modulus G ′ of the fluorine-containing elastomer was measured according to ASTM D6204 using a Rubber Process Analyzer (RPA2000, manufactured by Alpha Technology Co., Ltd.) at a sample amount of 7.5 g, a temperature of 100 ° C., and a displacement of 0.5 °. G ′ at 50 cpm when torque is measured by changing the frequency from 1 to 2000 cpm and G ′ and G ″ are calculated from the measured values.

<Measurement of storage elastic modulus E ′ and loss elastic modulus E ″>
The storage elastic modulus and loss elastic modulus of the fluororesin composition were obtained by cutting a test piece from a sheet having a length of 130 mm, a width of 130 mm, and a thickness of 1 mm prepared by preheating at 255 ° C. for 5 minutes and press forming for 5 minutes. (EXSTAR6000, manufactured by Seiko Instruments Inc.) was used for measurement. The storage elastic modulus and the loss elastic modulus are values measured at 250 ° C. in an air atmosphere. A test piece having a length of 45 mm, a width of 8 mm, and a thickness of 1 mm is taken as a tensile mode, a grip width = 20 mm, and a measurement temperature = 25 ° C. to 300 ° C. The measurement was performed under the conditions of ° C., temperature increase rate = 3 ° C./min, and frequency = 10 Hz. The storage elastic modulus E ′ and the loss elastic modulus E ″ are storage elastic modulus and loss elastic modulus at a temperature 25 ° C. higher than the melting point of the fluororesin, and the storage elastic modulus E ′ represents an elastic component, and the loss elastic modulus E ′. 'Represents a viscous component.

<Evaluation of properties on the surface of the molded body>
Extruder (MS30-25, manufactured by IK Corporation), screw (full flight, L / D = 24, φ30 mm, manufactured by IK Corporation), electric wire die cross head (maximum conductor diameter 3 mm, Maximum die hole diameter 20 mm, manufactured by Unitech Co., Ltd.), electric wire take-up machine (manufactured by Holy Seisakusho Co., Ltd.), winder (made by Holy Seisakusho Co., Ltd.), kneading temperature = 270 ° C., screw rotation speed = 35 rpm, take-up Under the condition of speed = 10 m / min, the fluororesin composition and the core wire (tin-plated copper wire, diameter 1.8 mm, constitution 37 / 0.26 mm (1 layer: 7 right-handed strands, 2 layer: 12 left-handed strands, An electric wire sample having a coating thickness of 0.5 mm and an electric wire diameter of 2.8 mm was obtained from 3 layers: 18 right-handed strands) manufactured by Yasuda Kogyo Co., Ltd. The surface roughness of the obtained wire sample was visually confirmed. A sample having no surface roughness and excellent surface smoothness was designated as “A”, and a sample having surface roughness and poor surface smoothness was designated as “B”.

<Measurement of minimum bending radius of tube>
It measured according to JIS B8381.

[Example 1]
Using a twin-screw extruder (KZW32TW-45MG-NH, manufactured by Technobel Co., Ltd., continuous type), 50 parts by mass of A1, 50 parts by mass of B1, and 1 part by mass of C1 were melt-kneaded and extruded to obtain a fluororesin composition. Obtained. The melt-kneading extrusion was performed under the condition of a screw rotation speed of 250 rpm and 240 ° C. for 2 minutes. Moreover, the twin screw extruder was provided with two kneading zones, and the ratio (L / D) of the total length L of the two kneading zones to the screw diameter D was 6.

[Example 2]
A fluororesin composition was obtained in the same manner as in Example 1 except that A2 was used instead of A1.

[Example 3]
A fluororesin composition was obtained in the same manner as in Example 1 except that the kneading temperature was 280 ° C.

[Example 4]
A fluororesin composition was obtained in the same manner as in Example 1 except that the kneading temperature was 300 ° C.

[Example 5]
A fluororesin composition was obtained in the same manner as in Example 4 except that B2 was used instead of B1.

[Example 6]
A fluororesin composition was obtained in the same manner as in Example 1 except that the amount of C1 used was 0.25 parts by mass.

[Example 7]
A fluororesin composition was obtained in the same manner as in Example 1 except that the amount of C1 used was 4 parts by mass.

[Example 8]
A fluororesin composition was obtained in the same manner as in Example 1 except that the screw speed in melt kneading extrusion was 150 rpm.

[Example 9]
A fluororesin composition was obtained in the same manner as in Example 1 except that the kneading temperature was 230 ° C.

[Example 10]
A fluororesin composition was obtained in the same manner as in Example 1 except that it was melt-kneaded and extruded using an internal mixer (Laboplast Mill KF70V2, manufactured by Toyo Seiki Co., Ltd., batch type).

  In the fluororesin composition obtained in each example, the fluorine-containing elastomer was dispersed in the fluororesin.

  Table 1 shows the storage elastic modulus E ′ and loss elastic modulus E ″ of the fluororesin composition obtained in each example. In the table, “ND” indicates that it was below the detection limit (100 kPa or less).

  As shown in Table 1, the wire sample obtained by dynamic molding using the fluororesin composition obtained in Example 1 which is the fluororesin composition of the present invention was excellent in surface smoothness. On the other hand, the fluororesin composition obtained in Example 8 has a high storage elastic modulus E ′ of the fluororesin composition, and the electric wire obtained by dynamic molding using the fluororesin composition obtained in Example 8 is used. The sample had a rough surface and was inferior in surface smoothness.

[Example 11]
Fluorine resin B3:
(1) A polymerization tank equipped with a stirrer having an internal volume of 430 liters is degassed, and 368.0 kg of CF ₃ CH ₂ O (CF ₂ ) ₂ H, 4.1 kg of methanol, CH ₂ = CH (CF ₂ ) ₂ 0.43 kg of F was charged, the temperature in the polymerization tank was raised to 66 ° C., and the pressure was increased to 1.5 MPa / G with a mixed gas of TFE and ethylene (TFE / ethylene = 89/11 (molar ratio)). As a polymerization initiator, 1993 g of a 2% CF ₃ CH ₂ O (CF ₂ ) ₂ H solution of tert-butyl peroxypivalate was charged to initiate polymerization. During the polymerization, a monomer mixed gas of TFE and ethylene (TFE / ethylene = 59/41 (molar ratio)) was continuously charged so that the pressure was constant. Further, CH ₂ ═CH (CF ₂ ) ₂ F in an amount corresponding to 0.6 mol% and IAH in an amount corresponding to 0.6 mol% are continuously added to the total number of moles of TFE and ethylene charged during the polymerization. I was charged. 255 minutes after the start of polymerization, when 22 kg of the monomer mixed gas was charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.
The obtained slurry-like fluorine-containing copolymer (B3-1) was put into an 860 L granulation tank charged with 340 kg of water, and the temperature was raised to 105 ° C. with stirring to distill and remove the solvent. Granulated. The obtained granulated product was dried at 150 ° C. for 15 hours to obtain 24.8 kg of a dry granulated product of the fluorinated copolymer (B3-1).
From the results of melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis of the fluorinated copolymer (B3-1), the fluorinated copolymer (B3-1) is obtained from TFE units / E units / The ratio of CH ₂ ═CH (CF ₂ ) ₂ F units / IAH units was 56.1 / 42.7 / 0.5 / 0.7 (molar ratio).
Moreover, MFR of the fluorine-containing copolymer (B3-1) was 33.7 g / 10min, and melting | fusing point was 256 degreeC.
(2) A polymerization tank equipped with a stirrer with an internal volume of 430 liters was degassed, 367.2 kg of CF ₃ CH ₂ O (CF ₂ ) ₂ H, 4.4 kg of methanol, CH ₂ = CH (CF ₂ ) ₂ 0.65 kg of F was charged, the temperature in the polymerization tank was raised to 66 ° C., and the pressure was increased to 1.5 MPa / G with a mixed gas of TFE and ethylene (TFE / ethylene = 89/11 (molar ratio)). As a polymerization initiator, 154 g of a 2% CF ₃ CH ₂ O (CF ₂ ) ₂ H solution of tert-butyl peroxypivalate was charged to initiate polymerization. During the polymerization, a monomer mixed gas of TFE and ethylene (TFE / ethylene = 59/41 (molar ratio)) was continuously charged so that the pressure was constant. Further, CH ₂ ═CH (CF ₂ ) ₂ F in an amount corresponding to 0.9 mol% with respect to the total mole number of TFE and ethylene charged during the polymerization was continuously charged. 494 minutes after the start of the polymerization, when 22 kg of the monomer mixed gas was charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.
The obtained slurry-like fluorine-containing copolymer (B3-2) was put into an 860 L granulation tank charged with 340 kg of water, and the temperature was raised to 105 ° C. with stirring to distill and remove the solvent. Granulated. The obtained granulated product was dried at 150 ° C. for 15 hours to obtain a dried granulated product of 25.0 kg of the fluorinated copolymer (B3-2).
From the results of melt NMR analysis, fluorine content analysis, and infrared absorption spectrum analysis of the fluorinated copolymer (B3-2), the fluorinated copolymer (B3-2) is TFE units / E units / The ratio of CH ₂ ═CH (CF ₂ ) ₂ F units was 57.5 / 41.7 / 0.8 (molar ratio).
Moreover, MFR of the fluorine-containing copolymer (B3-2) was 31.0 g / 10min, and melting | fusing point was 258 degreeC.
(3) 20 parts by mass of the granulated product (B3-1) and 80 parts by mass of the granulated product (B3-2) were dry blended, and then melt-kneaded using a twin-screw extruder with a residence time of 2 minutes. A pellet of fluororesin B3 was prepared.
Polyamide 12: Ube Industries, Ltd., trade name: UBESTA3030JLX2A

Polyamide 12 is supplied to the cylinder that forms the outer layer, fluororesin B3 is supplied to the cylinder that forms the intermediate layer, and the fluororesin composition obtained in Example 1 is supplied to the cylinder that forms the inner layer. Transported to the zone. The heating temperatures in the transport zone of polyamide 12, fluororesin B3 and the fluororesin composition obtained in Example 1 were 230 ° C., 300 ° C., and 300 ° C., respectively. Three-layer coextrusion was performed at a temperature of the common die of 320 ° C. to obtain a three-layer laminated tube. The outer diameter of this laminated tube is 8 mm, the inner diameter is 6 mm, and the thickness is 1 mm. The thickness of the outer layer of polyamide 12, the intermediate layer of fluororesin B3, and the inner layer of the fluororesin composition obtained in Example 1 is 0. They were 75 mm, 0.15 mm, and 0.1 mm. The inner layer and the intermediate layer, and the intermediate layer and the outer layer were extremely firmly adhered and did not peel off, and the peel strength could not be measured.
As a result of measuring the minimum bending radius of the obtained tube, it was 36 mm.

Polyamide 12 was supplied to the cylinder forming the outer layer, and fluororesin B3 was supplied to the cylinder forming the inner layer, and each was transferred to the transport zone of the cylinder. The heating temperatures in the transport zone of polyamide 12 and fluororesin B3 were 230 ° C. and 300 ° C., respectively. Two-layer coextrusion was performed at a temperature of the common die of 320 ° C. to obtain a two-layer laminated tube. The outer diameter of this laminated tube was 8 mm, the inner diameter was 6 mm, and the thickness was 1 mm. The thicknesses of the outer layer of polyamide 12 and the inner layer of fluororesin B3 were 0.8 mm and 0.2 mm, respectively. The inner layer and the outer layer were extremely firmly adhered and did not peel off, and the peel strength could not be measured.
As a result of measuring the minimum bending radius of the obtained tube, it was 42.5 mm.

The laminated tube obtained by molding using the fluororesin composition obtained in Example 1 which is the fluororesin composition of the present invention was excellent in bendability. On the other hand, the laminated tube not using the fluororesin composition of the present invention was inferior in bendability.
Note that Japanese Patent Application No. 2006-048759 filed on Mar. 11, 2016, Japanese Patent Application No. 2006-091850 filed on Apr. 28, 2016, and Japanese Patent Application filed on Sep. 16, 2016. The entire contents of the specification, claims and abstract of application No. 2006-182183 are hereby incorporated herein by reference as the disclosure of the specification of the present invention.

Claims (13)

A fluororesin composition comprising a melt-kneaded product comprising a fluorine-containing elastomer having a storage shear modulus G ′ of 100 or more and a melt-moldable fluororesin having a melting point of 150 ° C. or more,
The fluorine-containing elastomer is dispersed in the fluororesin,
The content of the fluorine-containing elastomer with respect to the total of the fluorine-containing elastomer and the fluorine resin is 10 to 65% by mass,
The total amount of the fluoroelastomer and the fluororesin is 90% by mass or more based on the fluororesin composition,
A fluororesin composition having a storage elastic modulus E ′ of 250 kPa or less at a temperature 25 ° C. higher than the melting point of the fluororesin. The fluororesin composition is a fluororesin composition comprising a melt-kneaded product containing an ethylene copolymer derived from an ethylene copolymer having an epoxy group, the fluoroelastomer and the fluororesin,
2. The fluororesin composition according to claim 1, wherein the content of the ethylene copolymer is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the fluoroelastomer and the fluororesin.   The fluororesin composition according to claim 1 or 2, wherein the fluorine-containing elastomer is a copolymer having units based on tetrafluoroethylene and units based on propylene.   The fluororesin composition according to any one of claims 1 to 3, wherein the fluorine-containing elastomer forms a sea-island structure or a co-continuous structure and is dispersed in the fluororesin.   The fluororesin is a polymer having a unit based on tetrafluoroethylene, a polymer having a unit based on vinylidene fluoride, or a polymer having a unit based on chlorotrifluoroethylene. Item 2. The fluororesin composition according to item.   The fluororesin composition according to claim 5, wherein the fluororesin is a copolymer having units based on ethylene and units based on tetrafluoroethylene.   The fluororesin composition of any one of Claims 1-6 whose melting | fusing point of the said fluororesin is 150-300 degreeC. A raw material containing a fluorine-containing elastomer having a storage shear modulus G ′ of 100 or more, a melt-moldable fluororesin having a melting point of 150 ° C. or more, and an ethylene copolymer having an epoxy group is melt-kneaded, cooled, and fluorine A method for producing a resin composition, comprising:
In the raw material before melt kneading, the content of the fluorine-containing elastomer with respect to the total of the fluorine-containing elastomer and the fluorine resin is 10 to 65% by mass, and the total amount of the fluorine-containing elastomer and the fluorine resin is, It is 90 mass% or more with respect to the said fluororesin composition, and the content of the ethylene copolymer which has the said epoxy group is 0-10 mass with respect to a total of 100 mass parts of the said fluorine-containing elastomer and the said fluororesin. Department,
After the melt kneading, the fluorine-containing elastomer is dispersed in the fluororesin, and the storage elastic modulus E ′ of the obtained fluororesin composition at a temperature 25 ° C. higher than the melting point of the fluororesin is 250 kPa. The manufacturing method of the fluororesin composition characterized by the following.   The method for producing a fluororesin composition according to claim 8, wherein the fluoroelastomer is dispersed in the fluororesin so as to form a sea-island structure or a co-continuous structure.   The molding material containing the fluororesin composition of any one of Claims 1-7.   The molded object formed by melt-molding the molding material of Claim 10.   A molded body composed of a single layer or multilayer film, sheet, hose or tube, wherein at least one of the layers in the molded body is a layer formed by melt molding of the molding material according to claim 10. Molded body.   A covered electric wire having a conductive wire and a covering material, wherein the covering material is a covering material formed by melt molding of the molding material according to claim 10.